JP6774032B2 - Resin composition, prepreg or resin sheet using the resin composition, laminated board and printed wiring board using them - Google Patents

Description

The present invention relates to a resin composition, a prepreg or resin sheet using the resin composition, a laminated board using the prepreg or the resin sheet, and a printed wiring board using the resin composition.

In recent years, as semiconductor packages widely used in electronic devices, communication devices, personal computers, etc. have become more sophisticated and smaller, the high integration and high-density mounting of each component for semiconductor packages has accelerated in recent years. ing. Along with this, the warp of the semiconductor plastic package caused by the difference in the coefficient of thermal expansion between the semiconductor element and the printed wiring board for the semiconductor plastic package has become a problem, and various measures have been taken.

One of the countermeasures is to reduce the thermal expansion of the insulating layer used for the printed wiring board. This is a method of suppressing warpage by bringing the coefficient of thermal expansion of a printed wiring board close to the coefficient of thermal expansion of a semiconductor element, and is currently being actively pursued (see, for example, Patent Documents 1 to 3).

As a method of suppressing the warp of the semiconductor plastic package, in addition to the low thermal expansion of the printed wiring board, the rigidity of the laminated board is increased (high rigidity) and the glass transition temperature of the laminated board is increased (high Tg). (See, for example, Patent Documents 4 and 5).

Japanese Unexamined Patent Publication No. 2013-216884 Japanese Patent No. 3173332 Japanese Unexamined Patent Publication No. 2009-035728 Japanese Unexamined Patent Publication No. 2013-001807 Japanese Unexamined Patent Publication No. 2011-178992

However, the low thermal expansion of the printed wiring board by the conventional method described in Patent Documents 1 to 3 is already approaching the limit, and further low thermal expansion is difficult.

On the other hand, the high rigidity of the laminated board is achieved by highly filling the resin composition used for the laminated board with a filler or by using an inorganic filler having a high elastic modulus such as alumina. However, there is a problem that the high filling of the filler deteriorates the moldability of the laminated plate, and the use of an inorganic filler such as alumina deteriorates the coefficient of thermal expansion of the laminated plate. Therefore, increasing the rigidity of the laminated board has not sufficiently achieved the suppression of warpage of the semiconductor plastic package.

In addition, the method of increasing the Tg of the laminated board improves the elastic modulus at the time of reflow, and is therefore effective in reducing the warp of the semiconductor plastic package. However, the method based on high Tg causes deterioration of moisture absorption and heat resistance due to an increase in crosslink density and generation of voids due to deterioration of moldability. Therefore, it is practically used in the field of electronic materials where extremely high reliability is required. Often problematic. Therefore, a method for solving these problems is desired.

Therefore, an object of the present invention is to provide a resin composition having a good elastic modulus maintenance rate and a low coefficient of thermal expansion.

As a result of diligent studies to solve the above problems, the present inventors have found that a resin composition containing a specific component has a good elastic modulus maintenance rate and a low coefficient of thermal expansion, and arrived at the present invention. ..

That is, the present invention relates to the following.
[1]
A resin composition containing an alkenyl-substituted nadiimide (A), a maleimide compound (B), and an amino-modified silicone (C).
[2]
The resin composition according to [1], wherein at least a part of the maleimide compound (B) is contained in the form of a prepolymer (P) polymerized with the amino-modified silicone (C).

[3]
The resin composition according to any one of [1] and [2], wherein the alkenyl-substituted nadiimide (A) contains a compound represented by the following general formula (1).
(In the formula (1), R ₁ independently represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or the following. Indicates a group represented by the general formula (2) or (3).)
(In formula (2), R ₃ represents a methylene group, an isopropylidene group, a substituent represented by CO, O, S, or SO _2. )
(In the formula (3), R ₄ independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)
[4]
The resin composition according to any one of [1] to [3], wherein the alkenyl-substituted nadiimide (A) contains a compound represented by the following formula (4) and / or a compound represented by the following formula (5). object.
[5]
The maleimide compound (B) is bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl). ) Any one of [1] to [4], which is at least one selected from the group consisting of methane, polytetramethylene oxide-bis (4-maleimidebenzoate) and a maleimide compound represented by the following general formula (6). The resin composition according to.
(In formula (6), R ₅ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)
[6]
The resin composition according to any one of [1] to [5], further comprising a cyanate ester compound.
[7]
The resin composition according to [6], wherein the cyanate ester compound contains a compound represented by the following formula (7) and / or a compound represented by the following formula (8).
(In formula (7), R ₆ independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)
(In formula (8), R ₇ independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.)
[8]
The resin composition according to any one of [1] to [7], further comprising an imidazole compound (X) represented by the following general formula (I).
In the formula (I), Ar is independently a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a hydroxyl group modified product thereof, and R is a hydrogen atom, an alkyl group or a hydroxyl group modified product thereof, or an aryl group. )
[9]
The resin composition according to [8], wherein the imidazole compound (X) represented by the general formula (I) is 2,4,5-triphenylimidazole.
[10]
The resin composition according to any one of [1] to [9], wherein the amino-modified silicone (C) contains a compound represented by the following general formula (Y).
(In formula (Y), R ₉ independently represents a hydrogen atom, a methyl group or a phenyl group, and R ₁₀ represents an alkylene group having 1 to 10 carbon atoms which may independently have a side chain. , N represents an integer greater than or equal to 0.)
[11]
The resin composition according to any one of [1] to [10], further comprising an inorganic filler (D).
[12]
The resin composition according to [11], wherein the inorganic filler (D) contains at least one selected from the group consisting of silica, alumina and aluminum nitride.
[13]
The content of the inorganic filler (D) is 50 to 500 parts by mass with respect to 100 parts by mass in total of the alkenyl-substituted nadiimide (A), the maleimide compound (B), and the amino-modified silicone (C) [11]. ] Or the resin composition according to [12].
[14]
A prepreg in which a base material is impregnated or coated with the resin composition according to any one of [1] to [13].
[15]
The prepreg according to [14], wherein the base material is at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fibers.
[16]
A resin sheet obtained by applying the resin composition according to any one of [1] to [13] to a support.
[17]
A laminated board containing a cured product of a laminated body in which at least one selected from the group consisting of the prepreg according to [14] and [15] and the resin sheet according to [16] is laminated.
[18]
A metal foil-clad laminate containing a cured product of a laminate obtained by laminating at least one selected from the group consisting of the prepregs described in [14] and [15] and the resin sheet described in [16] and a metal foil. ..
[19]
A printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, wherein the insulating layer contains the resin composition according to any one of [1] to [13]. Board.

According to the present invention, it is possible to provide a resin composition having a good elastic modulus maintenance rate and a low coefficient of thermal expansion.

Hereinafter, embodiments of the present invention (hereinafter, also referred to as “the present embodiment”) will be described. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments.

[Resin composition]
The resin composition of the present embodiment contains an alkenyl-substituted nadiimide (A), a maleimide compound (B), and an amino-modified silicone (C). Further, in the resin composition of the present embodiment, at least a part of the maleimide compound (B) is contained in the form of a prepolymer (P) polymerized with the amino-modified silicone (C) to improve the peel strength. , It is preferable in that it tends to improve desmear resistance, improve moldability, or suppress bleed-out of silicone component.
Hereinafter, the resin composition will be described in detail.

[Alkaline-substituted nadiimide (A)]
The alkenyl-substituted nadiimide (A) used in the present embodiment is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadiimide groups in the molecule. Specific examples thereof include compounds represented by the following general formula (1).

In the formula (1), R ₁ independently represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or the following general. The group represented by the formula (2) or (3) is shown.

In formula (2), R ₃ represents a methylene group, an isopropylidene group, a substituent represented by CO, O, S, or SO ₂ .

In the formula (3), R ₄ represents an independently selected alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.

Further, as the alkenyl-substituted nadiimide (A) represented by the formula (1), a commercially available product can also be used. Commercially available compounds are not particularly limited, but for example, a compound represented by the following formula (4) (BANI-M (manufactured by Maruzen Petrochemical Co., Ltd.)) and a compound represented by the following formula (5). (BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.)) and the like. These may be used alone or in combination of two or more.

In the resin composition of the present embodiment, the content of the alkenyl-substituted nadiimide (A) is not particularly limited, and the number of alkenyl groups (α) and maleimide, which are one of the functional groups of the alkenyl-substituted nadiimide (A) described later, are not particularly limited. It may be determined by the ratio of the number of functional groups to the number of maleimide groups (β) of the compound ([β / α]), but it is 10 to 60 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C). It is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass. By setting the content of the component (A) in such a range, the moldability is excellent even when the filler is filled, and the curability and thermal elastic modulus (for example, the flexural modulus at 250 ° C. and the flexural modulus at the solder reflow temperature) ), A printed wiring board having excellent desmear resistance and chemical resistance can be obtained. The ratio ([β / α]) of the alkenyl group number (α) of the alkenyl-substituted nadiimide (A) and the maleimide group number (β) of the maleimide compound (B) described above is preferably 0.9 to 4.3. It is more preferably .5 to 4.0, and even more preferably 1.5 to 3.0.

[Maleimide compound (B)]
The maleimide compound (B) used in the present embodiment is not particularly limited as long as it is a compound having one or more maleimide groups in the molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, and bis (3). , 5-Dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, polytetramethylene oxide-bis Examples thereof include (4-maleimide benzoate), a maleimide compound represented by the following formula (6), a prepolymer of these maleimide compounds, and a prepolymer of a maleimide compound and an amine compound. It is also possible to use one kind or a mixture of two or more kinds as appropriate.

Among them, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, polytetra. Methyl oxide-bis (4-maleimide benzoate), a maleimide compound represented by the following general formula (6) is preferable, and a maleimide compound represented by the following general formula (6) is particularly preferable. By including such a maleimide compound (B), the thermal expansion coefficient of the obtained cured product tends to decrease, the glass transition temperature tends to be improved, the heat resistance is improved, and the thermal elastic modulus tends to be improved.

In formula (6), R ₅ independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

In the formula, n ₁ represents an integer of 1 or more. The upper limit of n ₁ is preferably 10 and more preferably 7.

The resin composition of the present embodiment comprises a prepolymer (P) obtained by polymerizing a maleimide compound (B) and an amino-modified silicone (C), an alkenyl-substituted nadiimide (A), a maleimide compound (B), and the like. Is preferably included. Here, the maleimide compound (B) used as a raw material for the prepolymer (P) (hereinafter, also referred to as “maleimide compound (B-1)”) and the maleimide compound to be contained in the resin composition separately from the maleimide compound (B-1). The compound (B) (hereinafter, also referred to as “maleimide compound (B-2)”) may be the same or different, but is preferably different.
Examples of the maleimide compound (B-1) include bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, and bis (3-ethyl-5-methyl-4-). Maleimidephenyl) methane, polytetramethylene oxide-bis (4-maleimidebenzoate, a maleimide compound represented by the above general formula (6) is preferable, and 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane , Bis (3-ethyl-5-methyl-4-maleimidephenyl) methane is more preferred, and 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane is even more preferred.
Examples of the maleimide compound (B-2) include bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, and bis (3-ethyl-5-methyl-4-). Maleimidephenyl) methane, polytetramethylene oxide-bis (4-maleimidebenzoate), maleimide compounds represented by the above general formula (6) are preferable, and bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, Polytetramethylene oxide-bis (4-maleimidebenzoate), a maleimide compound represented by the following general formula (6) is more preferable, and a maleimide compound represented by the above general formula (6) is further preferable.
The maleimide compounds (B-1) and (B-2) may be used alone or in combination of two or more.
In the resin composition of the present embodiment, the content of the maleimide compound (B) is not particularly limited, and is the ratio of the number of alkenyl groups of the above-mentioned alkenyl-substituted nadiimide (A) to the number of maleimide groups of the maleimide compound (B). Although it may be determined by, it is preferably 30 to 80 parts by mass, more preferably 35 to 70 parts by mass, and 40 to 60 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C). It is more preferable to use parts by mass. When the above-mentioned maleimide compounds (B-1) and (B-2) are used as the maleimide compound (B) in the resin composition of the present embodiment, the content of the maleimide compound (B-1) is amino-modified silicone. It is determined by the number of amino groups in (C). That is, the ratio of the number of maleimide groups ([B-1 / C]) of the maleimide compound (B-1) to the number of amino groups of the amino-modified silicone (C) is preferably 1.0 to 20.0. It is more preferably ~ 15.0, and even more preferably 6.0 to 12.0. The content of the maleimide compound (B-2) is preferably the difference between the content of the maleimide compound (B) and the content of the maleimide compound (B-1) ([(B- (B-1)]). By setting the content of the component (B) in such a range, a printed wiring board having excellent moldability, curability, elastic modulus at heat, desmear resistance, and chemical resistance even when filled with a filler can be obtained. be able to.

[Amino-modified silicone (C)]
The amino-modified silicone (C) used in the present embodiment is not particularly limited as long as it is a compound having one or more amino groups in the molecule. Specific examples thereof include compounds represented by the following general formula (Y).

In the formula (Y), R ₉ independently represents a hydrogen atom, a methyl group or a phenyl group, and a methyl group is preferable. In the formula (Y), R ₁₀ represents an alkylene group having 1 to 10 carbon atoms which may independently have a side chain, and an alkylene group having 2 to 10 carbon atoms is preferable. In equation (Y), n represents an integer greater than or equal to 0.

The amino group equivalent of the transaminated silicone (C) is preferably 130 to 6000, more preferably 400 to 3000, and even more preferably 600 to 2500. By using such an amino-modified silicone (C), a resin composition having a good elastic modulus maintenance rate and a lower thermal expansion coefficient can be obtained.
In the resin composition of the present embodiment, the content of the amino-modified silicone (C) is not particularly limited, but is 1 to 40 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C). It is preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass. By setting the content of the component (C) in such a range, it is possible to obtain a resin composition having a good elastic modulus maintenance rate and a further lower thermal expansion rate.

[Other resins]
Further, in the resin composition of the present embodiment, it is possible to add another resin in addition to the above components (A) to (C) as long as the desired characteristics are not impaired. The type of the other resin is not particularly limited as long as it has insulating properties, and examples thereof include resins such as epoxy resins, benzoxazine compounds, phenol resins, and thermoplastic resins. By appropriately using these resins together, properties such as metal adhesion and stress relaxation property can be imparted.
For example, when an epoxy resin is used in combination, the epoxy resin is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and for example, bisphenol A type epoxy resin, bisphenol E type epoxy resin, and bisphenol. F-type epoxy resin, bisphenol S-type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, trifunctional phenol Type epoxy resin, tetrafunctional phenol type epoxy resin, glycidyl ester type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolac type epoxy resin, aralkyl novolac type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene Examples thereof include type epoxy resins, polyol type epoxy resins, isocyanurate ring-containing epoxy resins, and halides thereof. Among them, naphthylene ether type epoxy resin and biphenyl aralkyl type epoxy resin are more preferable from the viewpoint of glass transition temperature and heat resistance. The epoxy resin may be used alone or in combination of two or more.
The content of the epoxy resin is not particularly limited, but is preferably 3 to 40 parts by mass, more preferably 3 to 30 parts by mass, based on 100 parts by mass of the total of the components (A) to (C). More preferably, it is 3 to 20 parts by mass. When the content of the epoxy resin is within the above range, the heat resistance and curability tend to be further improved.

[Inorganic filler (D)]
Moreover, it is preferable that the resin composition of this embodiment further contains an inorganic filler (D).
The inorganic filler (D) used in the present embodiment is not particularly limited as long as it has insulating properties, and is, for example, silicas such as natural silica, molten silica, amorphous silica, and hollow silica, alumina, aluminum nitride, and boron nitride. , Boehmite, molybdenum oxide, titanium oxide, zinc borate, zinc tinate, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, glass short fibers (glass fine powders such as E glass and D glass) , Hollow glass, spherical glass and the like. These can be used alone or in admixture of two or more.

Among these, silica is preferably used from the viewpoint of low thermal expansion, and alumina or aluminum nitride is preferably used from the viewpoint of high thermal conductivity.

In the resin composition of the present embodiment, the content of the inorganic filler (D) is not particularly limited, but it is 50 to 500 parts by mass with respect to a total of 100 parts by mass of the components (A) to (C). It is preferable from the viewpoint of characteristics such as low thermal expansion and high thermal conductivity, and among them, 100 to 300 parts by mass is more preferable, and 100 to 250 parts by mass is further preferable.

[Cyanic acid ester compound]
The resin composition of the present embodiment preferably further contains a cyanate ester compound.
The type of the cyanate ester compound used in the present embodiment is not particularly limited, but for example, a naphthol aralkyl type cyanate ester represented by the following general formula (7) and a novolac type cyanic acid represented by the following general formula (8). Estel, biphenyl aralkyl type cyanate, bis (3,3-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-disyanatobenzene, 1,4-disyanatobenzene , 1,3,5-Trisianatobenzene, 1,3-disianatonaphthalene, 1,4-disianatonaphthalene, 1,6-disianatonaphthalene, 1,8-disianatonaphthalene, 2,6-disianatonaphthalene 2,7-Disianatonaphthalene, 1,3,6-trisianatonaphthalene, 4,4'-disianatobiphenyl, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis ( Examples thereof include 4-cyanatophenyl) sulfone, 2,2-bis (4-cyanatophenyl) propane, and prepolymers thereof. These may be used alone or in combination of two or more.

Among them, the naphthol aralkyl type cyanate ester compound represented by the following general formula (7), the novolak type cyanate ester represented by the following general formula (8), and the biphenyl aralkyl type cyanate ester are excellent in flame retardancy and are cured. It is particularly preferable because it has high properties and a low thermal expansion coefficient of the cured product.

In formula (7), R ₆ independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

In equation (7), n ₂ represents an integer of 1 or more. The upper limit of n ₂ is preferably 10 and more preferably 6.

In formula (8), R ₇ independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

In equation (8), n ₃ represents an integer of 1 or more. The upper limit of n ₃ is preferably 10 and more preferably 7.

The method for producing these cyanate ester compounds is not particularly limited, and any existing method for synthesizing cyanate ester may be used. Specifically, it can be obtained by reacting a naphthol aralkyl type phenol resin represented by the following general formula (9) with cyanogen halide in the presence of a basic compound in an inert organic solvent. It is also possible to adopt a method in which a similar naphthol aralkyl type phenol resin and a salt made of a basic compound are formed in a solution containing water, and then a two-phase interfacial reaction is carried out with cyanogen halide to synthesize the mixture. it can.

In formula (9), R ₈ independently represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

In equation (9), n ₄ represents an integer of 1 or more. The upper limit of n ₄ is preferably 10 and more preferably 6.

In addition, naphthol aralkyl-type cyanate ester compounds include naphthols such as α-naphthol or β-naphthol, p-xylene glycol, α, α'-dimethoxy-p-xylene, and 1,4-di (2-hydroxy-). It can be selected from those obtained by condensing naphthol aralkyl resin obtained by reaction with 2-propyl) benzene or the like and cyanic acid.

In the resin composition of the present embodiment, the content of the cyanate ester compound is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) to (C), and is 0.1. The amount is more preferably ~ 5 parts by mass, and further preferably 0.3 to 3 parts by mass. By setting the content of the cyanate ester compound within such a range, it is possible to obtain a printed wiring board having excellent moldability even when filled with a filler, and having excellent thermal elastic modulus, desmear resistance, and chemical resistance. ..

[Imidazole compound (X)]
The resin composition of the present embodiment preferably further contains the imidazole compound (X) represented by the following general formula (I).
In the formula (I), Ar is independently a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a hydroxyl group modified product thereof, and R is a hydrogen atom, an alkyl group or a hydroxyl group modified product thereof, or an aryl group. )
The imidazole compound (X) represented by the general formula (I) used in the present embodiment has an action of promoting curing and an action of raising the glass transition temperature of the cured product. Examples of the imidazole substituent Ar include a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a modified hydroxyl group thereof, and among them, a phenyl group is preferable. The imidazole substituent R is preferably an aryl group such as a hydrogen atom, an alkyl group or a modified hydroxyl group thereof, or a phenyl group, and further preferably a phenyl group for both the Ar group and the R group.
The imidazole compound (X) represented by the general formula (I) is preferably 2,4,5-triphenylimidazole from the viewpoint of the degree of curing and the glass transition temperature.

In the resin composition of the present embodiment, the content of the imidazole compound (X) represented by the general formula (I) is determined from the viewpoint of storage stability of the prepreg and moldability when processed into a copper-clad laminate. The range of 0.1 to 10 parts by mass is preferable, and the range of 0.2 to 5 parts by mass is particularly preferable with respect to 100 parts by mass of the total resin composition.

[Silicone powder]
The resin composition of the present embodiment may contain silicone powder. Silicone powder acts as a flame retardant aid that delays the burning time and enhances the flame retardant effect.
The silicone powder is not particularly limited, but for example, a fine powder of polymethylsilsesquioxane in which siloxane bonds are cross-linked in a three-dimensional network, and addition polymerization of vinyl group-containing dimethylpolysiloxane and methylhydrogenpolysiloxane. A fine powder of the product, a fine powder made of an addition polymer of vinyl group-containing dimethylpolysiloxane and methylhydrogenpolysiloxane, was coated with polymethylsilsesquioxane in which siloxane bonds were cross-linked in a three-dimensional network. Examples thereof include those in which the surface of the inorganic carrier is coated with polymethylsilsesquioxane in which siloxane bonds are crosslinked in a three-dimensional network. These are commercially available as silicone rubber powders and silicone composite powders.

The average particle size (D50) of the silicone powder is not particularly limited, but the average particle size (D50) is preferably 1 to 15 μm in consideration of dispersibility.

In the resin composition of the present embodiment, the content of the silicone powder is not particularly limited, but 3 to 120 parts by mass is preferable with respect to 100 parts by mass of the total of the components (A) to (C), and if it is too large, the moldability 3 to 60 parts by mass is particularly preferable because the dispersibility may be lowered.

[Silane coupling agent and wet dispersant]
In the resin composition of the present embodiment, a silane coupling agent or a wet dispersant can be used in combination in order to improve the dispersibility of the fine particles and the adhesive strength between the resin and the fine particles or the glass cloth. These silane coupling agents are not particularly limited as long as they are silane coupling agents generally used for surface treatment of inorganic substances. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, and γ. Acrylic silanes such as -acryloxypropyltrimethoxysilane, cyanicsilanes such as N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, phenylsilanes and the like can be mentioned. It is also possible to use one kind or a combination of two or more kinds as appropriate. The wet dispersant is not particularly limited as long as it is a dispersion stabilizer used for paints. Examples thereof include wet dispersants such as DISPER-110, 111, 118, 180, 161 and BYK-W996, W9010 and W903 manufactured by Big Chemy Japan Co., Ltd.

[Other curing accelerators]
Further, in the resin composition of the present embodiment, it is possible to use another curing accelerator in combination with the imidazole compound (X) as long as the desired characteristics are not impaired. Other curing accelerators are not particularly limited, but are exemplified by organic compounds such as benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, and di-tert-butyl-di-perphthalate. Oxides; azo compounds such as azobisnitrile; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, Tertiary amines such as quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidin; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, stearer Organic metal salts such as lead acid, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts are dissolved in hydroxyl group-containing compounds such as phenol and bisphenol. Inorganic metal salts such as tin chloride, zinc chloride and aluminum chloride; dioctyl tin oxide and other organic tin compounds such as alkyl tin and alkyl tin oxide can be mentioned.

〔solvent〕
Further, the resin composition of the present embodiment may contain a solvent, if necessary. For example, when an organic solvent is used, the viscosity at the time of preparing the resin composition is lowered, the handleability is improved, and the impregnation property into the glass cloth is improved. The type of solvent is not particularly limited as long as it can dissolve a part or all of the resin in the resin composition. Specific examples thereof include ketones such as acetone, methyl ethyl ketone and methyl cell solve, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, propylene glycol monomethyl ether and its acetate. , These are not particularly limited. As the solvent, one type can be used alone or two or more types can be used in combination.

[Manufacturing method of resin composition]
The resin composition of the present embodiment is produced, for example, by mixing the above-mentioned alkenyl-substituted nadiimide (A), maleimide compound (B), and amino-modified silicone (C), and if necessary, other optional components. be able to. In particular, in the resin composition of the present embodiment, the maleimide compound (B) and the amino-modified silicone (C) are polymerized to obtain a prepolymer (P), and the prepolymer (P) and the alkenyl-substituted nadiimide (A) are obtained. ), The maleimide compound (B), and if necessary, other optional components are preferably mixed from the viewpoints of peel strength, desmear resistance, moldability, bleed-out of silicone component, and the like. ..
The components (A) to (C) and optional components used in the method for producing the resin composition of the present embodiment are as described in the paragraph of the resin composition.

At the time of producing the resin composition of the present embodiment, an organic solvent can be used if necessary. The type of the organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.

At the time of producing the resin composition of the present embodiment, a known treatment (stirring, mixing, kneading treatment, etc.) for uniformly dissolving or dispersing each component can be performed. For example, when the inorganic filler (D) is used, the resin composition is subjected to the stirring and dispersing treatment by using a stirring tank equipped with a stirrer having an appropriate stirring ability for uniform dispersion of the inorganic filler (D). Dispersibility is enhanced. The above-mentioned stirring, mixing, and kneading treatment can be appropriately performed using, for example, an apparatus for mixing such as a ball mill or a bead mill, or a known apparatus such as a revolving or rotating type mixing apparatus.

[Prepreg]
The prepreg of the present embodiment is a prepreg impregnated or coated with the above resin composition on a base material.
The prepreg of the present embodiment can be obtained, for example, by combining the above resin composition with a base material, specifically, impregnating or coating the base material with the above resin composition. The method for producing the prepreg of the present embodiment can be carried out according to a conventional method, and is not particularly limited. For example, after impregnating or coating the base material with the above resin composition, the prepreg is semi-cured (B-staged) by heating in a dryer at 100 to 200 ° C. for 1 to 30 minutes. There is a way to obtain. In the present embodiment, the amount of the above resin composition (including the inorganic filler) with respect to the total amount of the prepreg is not particularly limited, but is preferably in the range of 30 to 90% by mass.

The base material used in the prepreg of the present embodiment is not particularly limited, and known materials used for various printed wiring board materials are appropriately selected and used according to the intended use and performance. be able to. Specific examples thereof include glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass and T glass, inorganic fibers other than glass such as quartz, and polyparaphenylene terephthalamide (Kevlar). (Registered trademark), Dupont Co., Ltd.), Copolyparaphenylene, 3,4'oxydiphenylene, terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Limited), etc. All aromatic polyamides, 2,6-hydroxy Examples include polyesters such as naphthoic acid and parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.), and organic fibers such as polyimide. However, it is not particularly limited to these.

Among these, E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fibers are preferable from the viewpoint of low thermal expansion.

These base materials may be used alone or in combination of two or more.

The shape of the base material is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surfaced mats. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones according to the intended use and performance. .. Further, a glass woven fabric obtained by opening the fibers or surface-treating with a silane coupling agent or the like is preferably used. The thickness and mass of the base material are not particularly limited, but usually those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a glass woven fabric having a thickness of 200 μm or less and a mass of 250 g / m ² or less, and a glass woven fabric made of glass fibers such as E glass, S glass, and T glass. Is more preferable.

[Laminated board using prepreg]
The laminated board of the present embodiment can be obtained, for example, by stacking one or more of the above-mentioned prepregs and curing them.
Further, the metal foil-clad laminate of the present embodiment can be obtained, for example, by laminating and curing the above-mentioned prepreg and the metal foil.
Specifically, the metal foil-clad laminate of the present embodiment can be obtained, for example, by laminating at least one or more of the above-mentioned prepregs and arranging metal foils on one side or both sides thereof. More specifically, by stacking one or more of the above-mentioned prepregs, and optionally arranging a metal foil such as copper or aluminum on one side or both sides of the prepreg, and laminating and molding this as necessary. , A metal foil-clad laminate can be manufactured. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The thickness of the metal foil is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm. The molding method of the metal foil-clad laminate and the molding conditions thereof are also not particularly limited, and general methods and conditions for the laminated plate for printed wiring boards and the multilayer plate can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when forming a metal foil-clad laminate. Further, in molding a metal foil-clad laminate, the temperature is generally in the range of 100 to 300 ° C., the pressure is generally in the range of ^{2 to} 100 kgf / cm ² , and the heating time is in the range of 0.05 to 5 hours. Further, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C. Further, it is also possible to form a multilayer plate by laminating and molding the above-mentioned prepreg and a wiring plate for an inner layer prepared separately.

The metal foil-clad laminate of the present embodiment can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate of the present embodiment has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effective as a printed wiring board for a semiconductor package in which such performance is required. Can be used.

Further, in the present embodiment, in addition to the above-mentioned prepreg form, the above-mentioned resin composition may be applied to a metal foil or a film to form an embedded sheet.

[Resin sheet]
The resin sheet of the present embodiment is a resin sheet in which the above-mentioned resin composition is applied to one side or both sides of a support. Here, the resin sheet is used as one means for thinning leaves. For example, a thermosetting resin (including an inorganic filler) used for prepreg or the like is directly attached to a support such as a metal foil or a film. Can be coated and dried to produce.

The support used in producing the resin sheet of the present embodiment is not particularly limited, but known materials used for various printed wiring board materials can be used. Examples thereof include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a polyethylene (PE) film, an aluminum foil, a copper foil, and a gold foil. Among them, electrolytic copper foil and PET film are preferable.

The resin sheet of the present embodiment is particularly preferably one in which the above-mentioned resin composition is applied to a support and then semi-cured (B-staged). As the method for producing the resin sheet of the present embodiment, a method for producing a composite of a B-stage resin and a support is generally preferable. Specifically, for example, the resin composition is applied to a support such as a copper foil and then semi-cured by heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes to produce a resin sheet. How to do it. The amount of the resin composition adhered to the support is preferably in the range of 1 to 300 μm in terms of the resin thickness of the resin sheet.

The resin sheet of this embodiment can be used as a build-up material for a printed wiring board.

[Laminated board using resin sheet]
The laminated board of the present embodiment can be obtained, for example, by stacking one or more of the above-mentioned resin sheets and curing them.
Further, the metal foil-clad laminate of the present embodiment can be obtained, for example, by laminating and curing the above-mentioned resin sheet and the metal foil.
Specifically, the metal foil-clad laminate of the present embodiment can be obtained, for example, by using the above-mentioned resin sheet and arranging metal foils on one side or both sides of the resin sheet to form the laminate. More specifically, for example, one of the above-mentioned resin sheets or a plurality of sheets having the support peeled off if desired are stacked, and a metal foil such as copper or aluminum is arranged on one side or both sides thereof. A metal foil-clad laminate can be manufactured by laminating and molding as needed. The metal foil used here is not particularly limited as long as it is used as a material for a printed wiring board, but a known copper foil such as a rolled copper foil or an electrolytic copper foil is preferable. The molding method of the metal foil-clad laminate and the molding conditions thereof are also not particularly limited, and general methods and conditions for the laminated plate for printed wiring boards and the multilayer plate can be applied. For example, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, or the like can be used when forming a metal foil-clad laminate. Further, when molding a metal foil-clad laminate, the temperature is generally in the range of 100 to 300 ° C., the pressure is generally in the range of ^{2 to} 100 kgf / cm ² , and the heating time is generally in the range of 0.05 to 5 hours. Further, if necessary, post-curing can be performed at a temperature of 150 to 300 ° C.

[Laminated board using resin sheet and prepreg]
The laminated board of the present embodiment may be a laminated board obtained by stacking one or more resin sheets and one or more prepregs and curing them, or by laminating and curing a resin sheet, a prepreg, and a metal foil. It may be a metal foil-covered laminated plate.

In the present embodiment, when the conductor layer to be a circuit is formed and the printed wiring board is produced, if the metal foil-clad laminate is not formed, the electroless plating method can also be used.

[Printed circuit board]
The printed wiring board of the present embodiment is a printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the above-mentioned resin composition.

The printed wiring board of the present embodiment is created, for example, by forming a conductor layer as a circuit on an insulating layer by metal foil or electroless plating. The conductor layer is generally composed of copper or aluminum. The insulating layer for a printed wiring board on which a conductor layer is formed can be suitably used for a printed wiring board by forming a predetermined wiring pattern. The printed wiring board of the present embodiment effectively warps the semiconductor plastic package by maintaining an excellent elastic modulus even under the reflow temperature at the time of semiconductor mounting because the insulating layer contains the above-mentioned resin composition. Since it is suppressed, it can be particularly effectively used as a printed wiring board for a semiconductor package.

Specifically, the printed wiring board of the present embodiment can be manufactured by, for example, the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared. An inner layer circuit is formed by etching the surface of a metal foil-clad laminate to prepare an inner layer substrate. The inner layer circuit surface of this inner layer substrate is subjected to surface treatment to increase the adhesive strength as necessary, then the required number of the above-mentioned prepregs are laminated on the inner layer circuit surface, and the metal foil for the outer layer circuit is laminated on the outer side thereof. Then, heat and pressurize to integrally mold. In this way, a multi-layer laminated board in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between an inner layer circuit and a metal foil for an outer layer circuit is manufactured. Next, after drilling holes for through holes and via holes in this multilayer laminated plate, desmear treatment is performed to remove smear, which is a resin residue derived from the resin component contained in the cured product layer. .. After that, a plated metal film that conducts the inner layer circuit and the metal foil for the outer layer circuit is formed on the wall surface of this hole, and the metal foil for the outer layer circuit is further etched to form the outer layer circuit, and the printed wiring board is manufactured. Will be done.

In the printed wiring board of the present embodiment, for example, the above-mentioned prepreg (the base material and the above-mentioned resin composition attached thereto), the above-mentioned resin sheet (the support and the above-mentioned resin composition attached thereto), and the like. The resin composition layer (layer made of the above-mentioned resin composition) of the metal foil-clad laminate constitutes an insulating layer containing the above-mentioned resin composition.

In the printed wiring board of the present embodiment, the difference between the flexural modulus at 25 ° C. and the flexural modulus during heat at 250 ° C. is preferably 20% or less, and more preferably 0 to 20%. It is preferably 0 to 15%, more preferably 0 to 15%. When the difference between the flexural modulus at 25 ° C. and the flexural modulus during heat at 250 ° C. is within the above range, the insulating layer has a good elastic modulus maintenance rate. Here, the elastic modulus maintenance rate means the ratio of the flexural modulus at 250 ° C. to the flexural modulus at 25 ° C.

In the present embodiment, the method for keeping the difference between the flexural modulus at 25 ° C. and the flexural modulus at the time of 250 ° C. of the insulating layer within 20% is not particularly limited, but for example, the resin used for the insulating layer. Examples thereof include a method of appropriately adjusting the type and content of each component of the composition within the above-mentioned range.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Synthesis Example 1] Synthesis of α-naphthol aralkyl type cyanogen ester resin A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser is previously cooled to 0 to 5 ° C. with brine, and chloride is added thereto. 7.47 g (0.122 mol) of cyanogen, 9.75 g (0.0935 mol) of 35% hydrochloric acid, 76 ml of water, and 44 ml of methylene chloride were charged.

-5 to + 5 ° C. The temperature of the reactor, while maintaining the pH at 1 or less, under stirring, wherein _{R 8} in (9) are all hydrogen atoms α- naphthol aralkyl type phenol resin (SN485, OH group equivalent : 214 g / eq. Softening point: 86 ° C., 20 g (0.0935 mol) manufactured by Nippon Steel Chemical Co., Ltd., and 14.16 g (0.14 mol) of triethylamine dissolved in 92 ml of methylene chloride were added by a dropping reactor. The mixture was added dropwise over time, and after completion of the addition, 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes.

After completion of the dropping, the mixture was stirred at the same temperature for 15 minutes, the reaction solution was separated, and the organic layer was separated. The obtained organic layer was washed twice with 100 ml of water, methylene chloride was distilled off under reduced pressure by an evaporator, and finally the mixture was concentrated to dryness at 80 ° C. for 1 hour to obtain cyanic acid, which is an α-naphthol aralkyl type phenol resin. An acid esterified product (α-naphthol aralkyl type cyanate ester resin), 23.5 g, was obtained.

[Example 1]
30 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 15 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, bisdiallyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.), 25 parts by mass, maleimide compound (BMI-2300, maleimide group equivalent 186 g / eq, Yamato Kasei) 30 parts by mass of Kogyo Co., Ltd., 5 parts by mass of epoxysilane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.), 1 part by mass of wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) , Wetting dispersant (DISPERBYK-111, manufactured by Big Chemie Japan Co., Ltd.) 0.5 parts by mass, slurry silica (SC-2050MB, manufactured by Admatex Co., Ltd.) 120 parts by mass, and 2,4,5-triphenyl. 0.5 parts by mass of imidazole (TPIZ, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to obtain a resin composition having a maleimide group number / amino group number ratio of 10.5 and a maleimide group number / alkenyl group number of 3.0.
In this example, the maleimide group number / amino group number and the maleimide group number / alkenyl group number are represented by the following formulas.
[Number of maleimide groups / number of amino groups] = (number of parts by mass of maleimide compound / equivalent of maleimide group of maleimide compound) / (number of parts by mass of diamino-modified silicone / amount of amino group equivalent of diamino-modified silicone)
[ Number of maleimide groups / number of alkenyl groups] = (number of parts by mass of maleimide compound / equivalent of maleimide group of maleimide compound) / (number of parts by mass of bisdiallyl nadiimide / equivalent number of alkenyl groups of bisdiallyl nadiimide)
A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 44.5% by mass.

[Example 2]
15 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 10 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, bisdiallyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.), 30 parts by mass, maleimide compound (BMI-2300, maleimide group equivalent 186 g / eq, Yamato Kasei) 35 parts by mass of Kogyo Co., Ltd., 5 parts by mass of epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.), 120 parts by mass of slurry silica (SC-2050MB, manufactured by Admatex Co., Ltd.), Biphenyl Aralkil type epoxy resin (NC3000FH, manufactured by Nippon Kayaku Co., Ltd.) 9.5 parts by mass, 2,2-bis (4-cyanatephenyl) propane prepolymer (CA210, manufactured by Mitsubishi Gas Chemicals) 0.5 parts by mass and 0.5 parts by mass of 2,4,5-triphenylimidazole (TPIZ, manufactured by Wako Pure Chemical Industries, Ltd.) was mixed to obtain a resin composition. A varnish was obtained by diluting the obtained resin composition having a maleimide group number / amino group number ratio of 7.9 and a maleimide group number / alkenyl group number of 2.3 with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 44.5% by mass.

[Example 3]
25 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 15 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, bisdiallyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.), 25 parts by mass, maleimide compound (BMI-2300, maleimide group equivalent 186 g / eq, Yamato Kasei) 30 parts by mass of Kogyo Co., Ltd., 5 parts by mass of epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.), 1 part by mass of wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) , Wetting dispersant (DISPERBYK-111, manufactured by Big Chemie Japan Co., Ltd.) 0.5 parts by mass, slurry silica (SC-2050MB, manufactured by Admatex Co., Ltd.) 120 parts by mass, biphenyl aralkyl type epoxy resin (NC3000FH, Japan) 4.5 parts by mass of chemicals (manufactured by Kayaku Co., Ltd.) and 0.5 parts by mass of prepolymer of 2,2-bis (4-cyanatephenyl) propane (CA210, manufactured by Mitsubishi Gas Chemicals) are mixed, and the number of maleimide groups / amino A resin composition having a group number ratio of 8.8 and a maleimide group number / alkenyl group number of 2.8 was obtained. A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 44.5% by mass.

[Example 4]
25 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 15 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, bisdiallyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.), 25 parts by mass, maleimide compound (BMI-2300, maleimide group equivalent 186 g / eq, Yamato Kasei) 30 parts by mass of Kogyo Co., Ltd., 5 parts by mass of epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.), 1 part by mass of wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) , Wet dispersant (DISPERBYK-111, manufactured by Big Chemie Japan Co., Ltd.) 0.5 parts by mass, slurry silica (SC-2050MB, manufactured by Admatex Co., Ltd.) 200 parts by mass, biphenyl aralkyl type epoxy resin (NC3000FH, Japan) 4.5 parts by mass of Kayaku Co., Ltd., 0.5 parts by mass of the α-naphthol aralkyl type cyanate ester resin obtained in Synthesis Example 1, and 2,4,5-triphenylimidazole (TPIZ, sum). (Manufactured by Kojun Yakuhin Co., Ltd.) 0.5 parts by mass was mixed to obtain a resin composition having a maleimide group number / amino group number ratio of 8.8 and a maleimide group number / alkenyl group number of 2.8. A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 47.0% by mass.

[Example 5]
25 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 15 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, bisdiallyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.) 25 parts by mass, maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 30 Parts by mass, epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.) 5 parts by mass, wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) 1 part by mass, wet dispersant (DISPERBYK- 111, 0.5 parts by mass of Big Chemie Japan Co., Ltd., 200 parts by mass of slurry silica (SC-2050MB, manufactured by Admatex Co., Ltd.), biphenyl aralkyl type epoxy resin (NC3000FH, manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass and 0.5 parts by mass of the α-naphthol aralkyl type cyanate resin obtained in Synthesis Example 1 were mixed to have a maleimide group number / amino group number ratio of 8.8 and a maleimide group number / alkenyl group number. A resin composition of 2.8 was obtained. A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 47.0% by mass.

[Example 6]
25 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 15 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, bisdiallyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.) 25 parts by mass, maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 30 Parts by mass, epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.) 5 parts by mass, wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) 1 part by mass, wet dispersant (DISPERBYK- 111, Big Chemy Japan Co., Ltd.) 0.5 parts by mass, Silicone composite powder (KMP-600, Shinetsu Chemical Industry Co., Ltd.) 20 parts by mass, Slurry silica (SC-2050MB, Admatex Co., Ltd.) 120 parts by mass, biphenyl aralkyl type epoxy resin (NC3000FH, manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass, and 2,2-bis (4-cyanatephenyl) propane prepolymer (CA210, manufactured by Mitsubishi Gas Chemicals) 0.5 parts by mass were mixed to obtain a resin composition having a maleimide group number / amino group number ratio of 8.8 and a maleimide group number / alkenyl group number of 2.8. A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 43.0% by mass.

[Comparative Example 1]
Bisdialyl nadiimide (BANI-M, alkenyl group equivalent 286 g / eq, manufactured by Maruzen Petrochemical Co., Ltd.) 45 parts by mass, maleimide compound (BMI-2300, maleimide group equivalent 186 g / eq, manufactured by Daiwa Kasei Kogyo Co., Ltd.) 45 parts by mass, epoxysilane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.), 5 parts by mass, wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.), 1 part by mass, slurry silica (SC- A resin composition was obtained by mixing 2050 MB, 120 parts by mass of Admatex Co., Ltd., and 10 parts by mass of the α-naphthol aralkyl type cyanate ester resin obtained in Synthesis Example 1 above. A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 44.5% by mass.

[Comparative Example 2]
15 parts by mass of maleimide compound (BMI-80, maleimide group equivalent 285 g / eq, manufactured by Keiai Kasei Co., Ltd.) and diamino-modified silicone (X-22-161B, amino group equivalent 1500 g / eq, Shinetsu Chemical Industry Co., Ltd.) (Manufactured) 10 parts by mass was polymerized to obtain a prepolymer. The obtained prepolymer, maleimide compound (BMI-70, maleimide group equivalent 221 g / eq, manufactured by Keiai Kasei Co., Ltd.), 10 parts by mass, maleimide compound (BMI-2300, maleimide group equivalent 186 g / eq, Daiwa Kasei Kogyo Co., Ltd.) 5 parts by mass of epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.), 3 parts by mass of wet dispersant (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.), Silicon resin powder (Tospearl, manufactured by Momentive Performance Materials Japan GK) 10 parts by mass, slurry silica (SC-2050MB, manufactured by Admatex Co., Ltd.) 120 parts by mass, biphenyl aralkyl type epoxy resin (NC3000FH, Japan) A resin composition was obtained by mixing 30 parts by mass of Yakuhin Co., Ltd. and 40 parts by mass of the α-naphthol aralkyl type cyanate ester resin obtained in Synthesis Example 1 above. A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 44.5% by mass.

[Comparative Example 3]
Maleimide compound (BMI-70, maleimide group equivalent 221 g / eq, manufactured by Keiai Kasei Co., Ltd.) 10 parts by mass, epoxy silane coupling agent (Z6040, manufactured by Toray Dow Coating Co., Ltd.) 5 parts by mass, wet dispersion Agent (DISPERBYK-161, manufactured by Big Chemie Japan Co., Ltd.) 3 parts by mass, silicon resin powder (Tospearl, manufactured by Momentive Performance Materials Japan LLC) 10 parts by mass, slurry silica (SC-2050MB, Admatex (manufactured by Admatex) (Manufactured by Co., Ltd.) 120 parts by mass, biphenyl aralkyl type epoxy resin (NC3000FH, manufactured by Nippon Kayaku Co., Ltd.) 40 parts by mass, α-naphthol aralkyl type cyanate ester resin 50 parts by mass and octyl obtained in the above synthesis example 1. A resin composition was obtained by mixing 0.05 parts by mass of zinc acid (Nikkaoctix zinc, manufactured by Nippon Kagaku Sangyo Co., Ltd.). A varnish was obtained by diluting the obtained resin composition with methyl ethyl ketone. This varnish was impregnated and coated on a 0.1 mm S glass woven fabric and dried by heating at 160 ° C. for 3 minutes to obtain a prepreg having a resin composition content of 44.5% by mass.

[Creation of metal foil laminated board]
The prepregs obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were stacked one or eight, respectively, and a 12 μm-thick electrolytic copper foil (3EC-III, manufactured by Mitsui Metal Mining Co., Ltd.) was placed one above the other. A copper-clad laminate having an insulating layer thickness of 0.8 mm was obtained by laminating and molding at a pressure of 30 kgf / cm ² and a temperature of 220 ° C. for 120 minutes.

Table 1 shows the results of measuring the flexural modulus, coefficient of thermal expansion, and solder heat resistance using the obtained copper-clad laminate.

[Method of evaluating physical properties of copper-clad laminate]

Bending elastic modulus: Using a sample of 50 mm × 25 mm × 0.8 mm, measurement was carried out at 25 ° C and 250 ° C by Autograph (AG-Xplus manufactured by Shimadzu Corporation) according to JIS standard C6481. ..

Elastic modulus retention rate: Calculated from the bending elastic modulus (a) at 25 ° C. and the thermal flexural modulus (b) at 250 ° C. measured by the above method by the following formula.

Elastic modulus maintenance rate (%) = (b) / (a) × 100

Coefficient of thermal expansion: Using a sample of 4.5 mm × 30 mm × 0.1 mm, heat the temperature from 40 ° C to 340 ° C at 10 ° C per minute with a thermomechanical analyzer (manufactured by TA Instruments), and from 60 ° C to 120. The coefficient of linear expansion in the plane direction at ° C was measured. The measurement direction was the vertical direction (Warp) of the glass cloth of the laminated plate.

Heat resistance evaluation: Evaluation was made by the following method using a copper foil-clad laminate.
Heat resistance: A sample of 50 × 50 mm was floated on 288 ° C. solder for 30 minutes, and the time until delamination occurred was measured. If delamination did not occur after 30 minutes, it was indicated as> 30 min in the table.

The resin composition of the present invention and a printed wiring board containing the resin composition can be suitably used as a member of various electronic devices such as personal computers and communication devices.

Claims (17)

Alkenyl-substituted nadiimide and (A),
Maleimide compound (B- 2 ) and
Comprising maleimide compound (B-1) and amino-modified silicone (C) and allowed to polymerize prepolymer obtained (P), and
The maleimide compound (B-1) is 2,2-bis (4- (4-maleimidephenoxy) -phenyl) propane and / or bis (3-ethyl-5-methyl-4-maleimidephenyl) methane. ,
A resin composition in which the maleimide compound (B-2) is a polytetramethylene oxide-bis (4-maleimide benzoate) and / or a maleimide compound represented by the general formula (6) .
(In formula (6), R ₅ independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more and 10 or less.) The resin composition according to claim 1, wherein the alkenyl-substituted nadiimide (A) contains a compound represented by the following general formula (1).
(In the formula (1), R ₁ independently represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or the following. Indicates a group represented by the general formula (2) or (3).)
(In formula (2), R ₃ represents a methylene group, an isopropylidene group, a substituent represented by CO, O, S, or SO _2. )
(In the formula (3), R ₄ independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.) The resin composition according to claim 1 or 2, wherein the alkenyl-substituted nadiimide (A) contains a compound represented by the following formula (4) and / or a compound represented by the following formula (5).
The resin composition according to any one of claims 1 to 3 , further comprising a cyanate ester compound. The resin composition according to claim 4 , wherein the cyanate ester compound contains a compound represented by the following formula (7) and / or a compound represented by the following formula (8).
(In formula (7), R ₆ independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.)
(In formula (8), R ₇ independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.) The resin composition according to any one of claims 1 to 5 , further comprising an imidazole compound (X) represented by the following general formula (I).
In the formula (I), Ar is independently a phenyl group, a naphthalene group, a biphenyl group, an anthracene group or a hydroxyl group modified product thereof, and R is a hydrogen atom, an alkyl group or a hydroxyl group modified product thereof, or an aryl group. ) The resin composition according to claim 6 , wherein the imidazole compound (X) represented by the general formula (I) is 2,4,5-triphenylimidazole. The resin composition according to any one of claims 1 to 7 , wherein the amino-modified silicone (C) contains a compound represented by the following general formula (Y).
(In the formula (Y), R ₉ independently represents a hydrogen atom, a methyl group or a phenyl group, and R ₁₀ represents an alkylene group having 1 to 10 carbon atoms which may independently have a side chain. , N represents an integer greater than or equal to 0.) The resin composition according to any one of claims 1 to 8 , further comprising an inorganic filler (D). The resin composition according to claim 9 , wherein the inorganic filler (D) contains at least one selected from the group consisting of silica, alumina and aluminum nitride. The content of the inorganic filler (D) is 100 parts by mass in total of the alkenyl-substituted nadiimide (A), the maleimide compound (B- 1 ), the maleimide compound (B-2), and the amino-modified silicone (C). The resin composition according to any one of claims 9 or 10 , which is 50 to 500 parts by mass. A prepreg in which a base material is impregnated or coated with the resin composition according to any one of claims 1 to 11 . The prepreg according to claim 12 , wherein the base material is at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth and organic fibers. A resin sheet obtained by applying the resin composition according to any one of claims 1 to 11 to a support. A laminated board containing a cured product of a laminated body in which at least one selected from the group consisting of the prepreg according to claims 12 and 13 and the resin sheet according to claim 14 is laminated. A metal foil-clad laminate containing a cured product of a laminate obtained by laminating at least one selected from the group consisting of the prepreg according to claims 12 and 13 and the resin sheet according to claim 14 and a metal foil. A printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, wherein the insulating layer contains the resin composition according to any one of claims 1 to 11. Board.